Process for production of living radical polymers and polymers

ABSTRACT

A process for producing a living radical polymer characterized in that a vinyl monomer is polymerized with use of a living radical polymerization initiator represented by the formula (1) and a compound represented by the formula (2), and the living radical polymer obtained by the process 
                         
wherein R 1  is C 1 -C 8  alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 2  and R 3  are each a hydrogen atom or C 1 -C 8  alkyl, and R 4  is aryl, substituted aryl, an aromatic heterocyclic group, acyl, oxycarbonyl or cyano
 (R 1 Te) 2   (2) 
wherein R 1  is the same as above.

CROSS REFERENCE

The present application is a divisional application of Ser. No.10/523,611, filed Feb. 7, 2005 now U.S. Pat. No. 7,291,690, which is a371 application of PCT/JP2003/010116, filed Aug. 8, 2003.

TECHNICAL FIELD

The present invention relates to a process for producing living radicalpolymers and the living radical polymers obtained by the process.

BACKGROUND ART

Living radical polymerization is a polymerization process which isadapted for precision control of molecular structures while ensuringconvenience and universal usefulness of radical polymerization, and ispowerful means for preparing novel polymer materials. Georges et al hasmade a report on a typical example of living radical polymerizationusing TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) as an initiator(publication of JP-A No. 1994-199916).

This process makes it possible to control molecular weights andmolecular weight distributions, but requires a high polymerizationtemperature of 130° C. and is difficult to use for monomers having athermally unstable functional group. The process is also unsuited to thecontrol of modification of terminal functional groups of high molecularweight compounds.

An object of the present invention is to provide a process for producinga living radical polymer by polymerizing a vinyl monomer with use of anorganotellurium compound represented by the formula (1) and a compoundrepresented by the formula (2), the process making possible precisioncontrol of molecular weights and molecular weight distributions(PD=Mw/Mn) under mild conditions, and the polymer.

DISCLOSURE OF THE INVENTION

The present invention provides a process for producing a living radicalpolymer characterized in that a vinyl monomer is polymerized with use ofa living radical polymerization initiator represented by the formula (1)and a compound represented by the formula (2), and the living radicalpolymer obtained by the process

wherein R¹ is C₁-C₈ alkyl, aryl, substituted aryl or an aromaticheterocyclic group, R² and R³ are each a hydrogen atom or C₁-C₈ alkyl,and R⁴ is aryl, substituted aryl, an aromatic heterocyclic group, acyl,oxycarbonyl or cyano(R¹Te)₂  (2)wherein R¹ is the same as above.

The living radical polymer of the present invention is produced bypolymerizing a vinyl monomer in the presence of a compound representedby the formula (2) using a living radical polymerization initiatorrepresented by the formula (1)

wherein R¹ is C₁-C₈ alkyl, aryl, substituted aryl or an aromaticheterocyclic group, R² and R³ are each a hydrogen atom or C₁-C₈ alkyl,and R⁴ is aryl, substituted aryl, an aromatic heterocyclic group, acyl,oxycarbonyl or cyano(R¹Te)₂  (2)wherein R¹ is the same as above.

The living radical polymerization initiator to be used in the presentinvention is a compound represented by the formula (1).

Examples of groups represented by R¹ are as follows.

Examples of C₁-C₈ alkyl groups usable are straight-chain, branched chainor cyclic alkyl groups having 1 to 8 carbon atoms, such as methyl,ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl,cyclobutyl, n-pentyl, n-hexyl, n-heptyl and n-octyl. Preferable alkylgroups are straight-chain or branched chain alkyl groups having 1 to 4carbon atoms. Methyl or ethyl is more preferable.

Examples of groups usable include aryl groups such as phenyl andnaphthyl, substituted aryl groups such as phenyl having a substituentand naphthyl having a substituent, and aromatic heterocyclic groups suchas pyridyl, furyl and thienyl. Examples of substituents of aryl groupshaving a substituent are a halogen atom, hydroxyl, alkoxyl, amino,nitro, cyano, carbonyl-containing groups represented by —COR⁵ (R⁵═C₁-C₈alkyl, aryl, C₁-C₈ alkoxyl or aryloxy), sulfonyl, trifluoromethyl, etc.Preferable aryl groups are phenyl and trifluoromethyl-substitutedphenyl. Preferably such substituted groups have one or two substituentsat the para-position or ortho-position.

Examples of groups represented by R² and R³ are as follows.

Examples of C₁-C₈ alkyl groups usable are the same as the alkyl groupsrepresented by R¹ and given above.

Examples of groups represented by R⁴ are as follows.

Examples of aryl, substituted aryl, aromatic heterocyclic groups usableare the same as those groups represented by R¹ and given above.

Examples of acyl groups usable are formyl, acetyl, benzoyl, etc.

Examples of preferred oxycarbonyl groups are those represented by —COOR⁶(R⁶═H, C₁-C₈ alkyl or aryl) such as carboxyl, methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl,tert-butoxycarbonyl, n-pentoxycarbonyl and phenoxycabonyl.Methoxycarbonyl and ethoxycarbonyl are more desirable oxycarbonylgroups.

Examples of preferred groups represented by R⁴ are aryl, substitutedaryl and oxycarbonyl. The aryl group is preferably phenyl. Examples ofpreferred substituted aryl groups are phenyl substituted with a halogenatom and phenyl substituted with trifluoromethyl. When the substituentis a halogen, the phenyl is substituted with preferably one to fivehalogen atoms. In the case of alkoxyl or trifluoromethyl, preferably oneor two substituents are present. When having one substituent, the groupis substituted preferably at the para- or ortho-position. When the grouphas two substituents, the meta-positions are preferred. Examples ofpreferred oxycarbonyl groups are methoxycarbonyl and ethoxycarbonyl.

Examples of preferred organotellurium compounds represented by theformula (1) are compounds wherein R¹ is C₁-C₄ alkyl, R² and R³ are eacha hydrogen atom or C₁-C₄ alkyl, and R⁴ is aryl, substituted aryl oroxycarbonyl. More preferable organotellurium compounds are those whereinR¹ is C₁-C₄ alkyl, R² and R³ are each a hydrogen atom or C₁-C₄ alkyl,and R⁴ is phenyl, substituted phenyl, methoxycarbonyl or ethoxycarbonyl.

Examples of organotellurium compounds represented by the formula (1) areas follows.

Such organotellurium compounds are preferably(methyltellanyl-methyl)benzene, (1-methyltellanyl-ethyl)benzene,(2-methyltellanyl-propyl)benzene,1-chloro-4-(methyltellanyl-methyl)benzene,1-hydroxy-4-(methyltellanyl-methyl)benzene,1-methoxy-4-(methyltellanyl-methyl)benzene,1-amino-4-(methyltellanyl-methyl)benzene,1-nitro-4-(methyltellanyl-methyl)benzene,1-cyano-4-(methyltellanyl-methyl)benzene,1-methylcarbonyl-4-(methyltellanyl-methyl)benzene,1-phenylcarbonyl-4-(methyltellanyl-methyl)benzene,1-methoxycarbonyl-4-(methyltellanyl-methyl)benzene,1-phenoxycarbonyl-4-(methyltellanyl-methyl)benzene,1-sulfonyl-4-(methyltellanyl-methyl)benzene,1-trifluoromethyl-4-(methyltellanyl-methyl)benzene,1-chloro-4-(1-methyltellanyl-ethyl)benzene,1-hydroxy-4-(1-methyltellanyl-ethyl)benzene,1-methoxy-4-(1-methyltellanyl-ethyl)benzene,1-amino-4-(1-methyltellanyl-ethyl)benzene,1-nitro-4-(1-methyltellanyl-ethyl)benzene,1-cyano-4-(1-methyltellanyl-ethyl)benzene,1-methylcarbonyl-4-(1-methyltellanyl-ethyl)benzene,1-phenylcarbonyl-4-(1-methyltellanyl-ethyl)benzene,1-methoxycarbonyl-4-(1-methyltellanyl-ethyl)benzene,1-phenoxycarbonyl-4-(1-methyltellanyl-ethyl)benzene,1-sulfonyl-4-(1-methyltellanyl-ethyl)benzene,1-trifluoromethyl-4-(1-methyltellanyl-ethyl)benzene[1-(1-methyltellanyl-ethyl)-4-trifluoromethylbenzene],1-(1-methyltellanyl-ethyl)-3,5-bis-trifluoromethylbenzene,1,2,3,4,5-pentafluoro-6-(1-methyltellanyl-ethyl)benzene,1-chloro-4-(2-methyltellanyl-ethyl)benzene,1-hydroxy-4-(2-methyltellanyl-propyl)benzene,1-methoxy-4-(2-methyltellanyl-propyl)benzene,1-amino-4-(2-methyltellanyl-propyl)benzene,1-nitro-4-(2-methyltellanyl-propyl)benzene,1-cyano-4-(2-methyltellanyl-propyl)benzene,1-methylcarbonyl-4-(2-methyltellanyl-propyl)benzene,1-phenylcarbonyl-4-(2-methyltellanyl-propyl)benzene,1-methoxycarbonyl-4-(2-methyltellanyl-propyl)benzene,1-phenoxycarbonyl-4-(2-methyltellanyl-propyl)benzene,1-sulfonyl-4-(2-methyltellanyl-propyl)benzene,1-trifluoromethyl-4-(2-methyltellanyl-propyl)benzene,2-(methyltellanyl-methyl)pyridine, 2-(1-methyltellanyl-ethyl)pyridine,2-(2-methyltellanyl-propyl)pyridine, 2-methyl-2-methyltellanyl-propanal,3-methyl-3-methyltellanyl-2-butanone, methyl 2-methyltellanyl-ethanate,methyl 2-methyltellanyl-propionate, methyl2-methyltellanyl-2-methylpropionate, ethyl 2-methyltellanyl-ethanate,ethyl 2-methyltellanyl-propionate, ethyl2-methyltellanyl-2-methylpropionate[ethyl-2-methyl-2-methyltellanyl-propionate], ethyl2-(n-butyltellanyl)-2-methylpropionate[ethyl-2-methyl-2-n-butyltellanyl-propionate],2-methyltellanylacetonitrile, 2-methyltellanyl-propionitrile,2-methyl-2-methyltellanyl-propionitrile, (phenyltellanyl-methyl)benzene,(1-phenyltellanyl-ethyl)benzene, (2-phenyltellanyl-propyl)benzene, etc.The above compounds also include all compounds having ethyltellanyl,1-ethyllellanyl, 2-ethyltellanyl, butyltellanyl, 1-butyltellanyl or2-butyltellanyl, as changed from the portion of methyltellanyl,1-methyltellanyl or 2-methyltellanyl. Preferable are(methyltellanyl-methyl)benzene, (1-methyltellanyl-ethyl)benzene,(2-methyltellanyl-propyl)benzene,1-chloro-4-(1-methyltellanyl-ethyl)benzene,1-trifluoromethyl-4-(1-methyltellanyl-ethyl)benzene[1-(1-methyltellanyl-ethyl)-4-trifluoromethylbenzene], methyl2-methyltellanyl-2-methylpropionate, ethyl2-methyltellanyl-2-methylpropionate[ethyl-2-methyl-2-methyltellanyl-propionate], ethyl2-(n-butyltellanyl)-2-methylpropionate[ethyl-2-methyl-2-n-butyltellanyl-propionate],1-(1-methyltellanyl-ethyl)-3,5-bis-trifluoromethylbenzene,1,2,3,4,5-pentafluoro-6-(1-methyltellanyl-ethyl)benzene,2-methyltellanyl-propionitrile, 2-methyl-2-methyltellanylpropionitrile,(ethyltellanyl-methyl)benzene, (1-ethyltellanyl-ethyl)benzene,(2-ethyltellanyl-propyl)benzene, methyl2-ethyltellanyl-2-methylpropionate, ethyl2-ethyltellanyl-2-methylpropionate, 2-ethyltellanyl-propionitrile,2-methyl-2-ethyltellanylpropionitrile, (n-butyltellanyl-methyl)benzene,(1-n-butyltellanyl-ethyl)benzene, (2-n-butyltellanyl-propyl)benzene,methyl 2-n-butyltellanyl-2-methylpropionate, ethyl2-n-butyltellanyl-2-methylpropionate, 2-n-butyltellanyl-propionitrile,2-methyl-2-n-butyltellanyl-propionitrile.

The living radical polymerization initiator represented by the formula(1) can be prepared by reacting a compound of the formula (3), acompound of the formula (4) and metallic tellurium.

Examples of compounds represented by the formula (3) are as follows.

wherein R², R³ and R⁴ are as defined above, and X is a halogen atom.

Examples of groups represented by R², R³ and R⁴ are as given above.

Examples of groups represented by X can be a halogen atom such asfluorine, chlorine, bromine or iodine. Chlorine and bromine arepreferable.

Examples of compounds usable are benzyl chloride, benzyl bromide,1-chloro-1-phenylethane, 1-bromo-1-phenylethane,2-chloro-2-phenylpropane, 2-bromo-2-phenylpropane, p-chlorobenzylchloride, p-hydroxybenzyl chloride, p-methoxybenzyl chloride,p-aminobenzyl chloride, p-nitrobenzyl chloride, p-cyanobenzyl chloride,p-methylcarbonylbenzyl chloride, phenylcarbonylbenzyl chloride,p-methoxycarbonylbenzyl chloride, p-phenoxycarbonylbenzyl chloride,p-sulfonylbenzyl chloride, p-trifluoromethylbenzyl chloride,1-chloro-1-(p-chlorophenyl)ethane, 1-bromo-1-(p-chlorophenyl)ethane,1-chloro-1-(p-hydroxyphenyl)ethane, 1-bromo-1-(p-hydroxyphenyl)-ethane,1-chloro-1-(p-methoxyphenyl)ethane, 1-bromo-1-(p-methoxyphenyl)ethane,1-chloro-1-(p-aminophenyl)ethane, 1-bromo-1-(p-aminophenyl)ethane,1-chloro-1-(p-nitrophenyl)ethane, 1-bromo-1-(p-nitrophenyl)ethane,1-chloro-1-(p-cyanophenyl)ethane, 1-bromo-1-(p-cyanophenyl)ethane,1-chloro-1-(p-methylcarbonylphenyl)ethane,1-bromo-1-(p-methylcarbonylphenyl)ethane,1-chloro-1-(p-phenylcarbonylphenyl)ethane,1-bromo-1-(p-phenylcarbonylphenyl)-ethane,1-chloro-1-(p-methoxycarbonylphenyl)ethane,1-bromo-1-(p-methoxycarbonylphenyl)ethane,1-chloro-1-(p-phenoxycarbonylphenyl)-ethane,1-bromo-1-(p-phenoxycarbonylphenyl)ethane,1-chloro-1-(p-sulfonylphenyl)ethane, 1-bromo-1-(p-sulfonylphenyl)ethane,1-chloro-1-(p-trifluoromethylphenyl)ethane,1-bromo-1-(p-trifluoromethylphenyl)ethane,2-chloro-2-(p-chlorophenyl)propane, 2-bromo-2-(p-chlorophenyl)propane,2-chloro-2-(p-hydroxyphenyl)-propane,2-bromo-2-(p-hydroxyphenyl)propane, 2-chloro-2-(p-methoxyphenyl)propane,2-bromo-2-(p-methoxyphenyl)propane, 2-chloro-2-(p-aminophenyl)propane,2-bromo-2-(p-aminophenyl)propane, 2-chloro-2-(p-nitrophenyl)propane,2-bromo-2-(p-nitrophenyl)-propane, 2-chloro-2-(p-cyanophenyl)propane,2-bromo-2-(p-cyanophenyl)propane,2-chloro-2-(p-methylcarbonylphenyl)propane,2-bromo-2-(p-methylcarbonylphenyl)propane,2-chloro-2-(p-phenylcarbonylphenyl)propane,2-bromo-2-(p-phenylcarbonylphenyl)-propane,2-chloro-2-(p-methoxycarbonylphenyl)propane,2-bromo-2-(p-methoxycarbonylphenyl)propane,2-chloro-1-(p-phenoxycarbonylphenyl)propane,2-bromo-2-(p-phenoxycarbonylphenyl)propane,2-chloro-2-(p-sulfonylphenyl)propane,2-bromo-2-(p-sulfonylphenyl)propane,2-chloro-2-(p-trifluoromethylphenyl)propane,2-bromo-2-(p-trifluoromethylphenyl)propane, 2-(chloromethyl)pyridine,2-(bromomethyl)pyridine, 2-(1-chloroethyl)pyridine,2-(1-bromoethyl)pyridine, 2-(2-chloropropyl)pyridine,2-(2-bromopropyl)pyridine, methyl 2-chloroethanoate, methyl2-bromoethanoate, methyl 2-chloropropionate, methyl 2-bromoethanoate,methyl 2-chloro-2-methylpropionate, methyl 2-bromo-2-methylpropionate,ethyl 2-chloroethanoate, ethyl 2-bromoethanoate, ethyl2-chloropropionate, ethyl 2-bromoethanoate, ethyl2-chloro-2-ethylpropionate, ethyl 2-bromo-2-ethylpropionate,2-chloroacetonitrile, 2-bromoacetonitrile, 2-chloropropionitrile,2-bromopropionitrile, 2-chloro-2-methylpropionitrile,2-bromo-2-methylpropionitrile, (1-bromoethyl)benzene,ethyl-2-bromo-iso-butylate, 1-(1-bromoethyl)-4-chlorobenzene,1-(1-bromoethyl)-4-trifluoromethylbenzene,1-(1-bromoethyl)-3,5-bis-trifluoromethylbenzene,1,2,3,4,5-pentafluoro-6-(1-bromoethyl)benzene,1-(1-bromoethyl)-4-methoxybenzene, ethyl-2-bromo-isobutylate, etc.

Examples of compounds represented by the formula (4) are as follows.M(R¹)m  (4)wherein R¹ is as defined above, M is an alkali metal, alkaline earthmetal or copper atom, and m is 1 when M is an alkali metal, m is 2 whenM is an alkaline earth metal, or m is 1 or 2 when M is a copper atom.

Examples of groups represented by R¹ are as given above.

Examples of metals represented by M are lithium, sodium, potassium andlike alkali metals, magnesium, calcium and like alkaline earth metals,and copper. Lithium is desirable.

In case that M is magnesium, the compound (4) may either be Mg(R¹)₂ or acompound represented by MgX (X is a halogen atom) which is a Grignardreagent. Chlorine and bromine are preferable.

Examples of compounds usable are methyllithium, ethyllithium,n-butyllithium, phenyllithium, p-methoxyphenyl-lithium, etc.Methyllithium, ethyllithium, n-butyllithium and phenyllithium arepreferable.

Next, a detailed description will be given of the process for preparingthe compound.

Metallic tellurium is suspended in a solvent. Examples of solventsusable are dimethylformamide (DMF), tetrahydrofuran (THF) and like polarsolvents, toluene, xylene and like aromatic solvents, hexane and likealiphatic hydrocarbons, dialkyl ethers and like ethers, etc. THF ispreferable. The amount of solvent to be used, which is suitablyadjusted, is 1 to 100 ml, preferably 5 to 10 ml, per gram of metallictellurium.

A compound (4) is slowly added dropwise to the suspension, followed bystirring. The reaction time differs with the reaction temperature andpressure and is usually 5 minutes to 24 hours, preferably 10 minutes to2 hours. The reaction temperature is −20° C. to 80° C., preferably 15°C. to 40° C., more preferably room temperature. The reaction isconducted usually under atmospheric pressure, but may be conducted atincreased pressure or in a vacuum.

Next, a compound (3) is added to the reaction mixture, followed bystirring. The reaction time differs with the reaction temperature andpressure and is usually 5 minutes to 24 hours, preferably 10 minutes to2 hours. The reaction temperature is −20° C. to 80° C., preferably 15°C. to 40° C., more preferably room temperature. The reaction isconducted usually under atmospheric pressure, but may be conducted atincreased pressure or in a vacuum.

The proportions of the compound (3) and compound (4) to metallictellurium are 0.5 to 1.5 moles of the compound (3) and 0.5 to 1.5 molesof the compound (4), preferably 0.8 to 1.2 moles of the compound (3) and0.8 to 1.2 moles of the compound (4), per mole of metallic tellurium.

After the completion of the reaction, the solvent is concentrated, andthe desired compound is isolated and purified. Although the method ofpurification can be determined suitably depending on the compound,usually vacuum distillation or recrystallization is preferable.

The vinyl monomer to be used in the present invention is notparticularly limited insofar as the monomer can be subjected to radicalpolymerization. Examples of vinyl monomers usable are methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl(meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate,(meth)acrylic acid 2-hydroxyethyl ester [2-hydroxyethyl(meth)acrylate]and like (meth)acrylic acid esters, cyclohexyl (meth)acrylate,methylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, cyclododecyl(meth)acrylate and like cycloalkyl-containing unsaturated monomers,(meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconicacid, crontonic acid, maleic anhydride and like carboxyl-containingunsaturated monomers, N,N-dimethylaminopropyl(meth)acrylamide,N,N-dimethylaminoethyl(meth)acrylamide, 2-(dimethylamino)ethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate and likeunsaturated monomers containing a tertiary amine,N-2-hydroxy-3-acryloyloxypropyl-N,N,N-trimethylammonium chloride,N-methacryloylaminoethyl-N,N,N-dimethylbenzylammonium chloride and likeunsaturated monomers containing quaternary ammonium base, glycidyl(meth)acrylate and like epoxy-containing unsaturated monomers, styrene,α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene,4-methoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene,4-chlorostyrene, 2,4-dichlorostyrene, 1-vinylnaphthalene,divinylbenzene, p-styrenesulfonic acid or an alkali metal salt thereof(sodium salt or potassium salt, etc.) and like aromatic unsaturatedmonomers (styrene type monomer), 2-vinylthiophene,N-methyl-2-vinylpyrrole and like unsaturated monomers containing aheterocyclic ring, N-vinylformaldehyde, N-vinylacetamide and likevinylamides, 1-hexane, 1-octene, 1-decene and like α-olefins, butadiene,isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and likedienes, methyl vinyl ketone, ethyl vinyl ketone and like unsaturatedmonomers containing a carbonyl group, vinyl acetate, vinyl benzoate,hydroxyethyl (meth)acrylate, (meth)acrylonitrile, (meth)acrylamide,N-methyl(meth)acrylamide, N-isopropyl-(meth)acrylamide,N,N-dimethyl(meth)acrylamide and like (meth)acrylamide type monomers,vinyl chloride, etc.

Preferable among these are (meth)acrylic acid ester monomers,unsaturated monomers containing a tertiary amine, aromatic unsaturatedmonomers (styrene type monomers), unsaturated monomers containing acarbonyl group, acrylamide, (meth)acrylamide and N,N-dimethylacrylamide.Particularly preferable are (meth)acrylic acid ester monomers, aromaticunsaturated monomers (styrene type monomers), unsaturated monomerscontaining a carbonyl group, (meth)acrylonitrile, (meth)acrylamide typemonomers.

Examples of preferable (meth)acrylic acid ester monomers are methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl(meth)acrylate and (meth)acrylic acid 2-hydroxyethyl ester[2-hydroxyethyl(meth)acrylate]. Especially preferable are methyl(meth)acrylate and butyl (meth)acrylate. Among these preferable aremethyl methacrylate, ethyl methacrylate, propyl methacrylate, butylmethacrylate and methacrylic acid 2-hydroxyethyl ester [2-hydroxyethylmethacrylate].

Examples of preferable unsaturated monomers containing a tertiary amineare N,N-dimethylaminoethyl(meth)acrylamide and2-(dimethylamino)ethyl(meth)acrylate.

Examples of preferable styrene type monomers are styrene,α-methylstyrene, o-methylstyrene, p-methylstyrene, p-methoxystyrene,p-t-butylstyrene, p-n-butylstyrene p-chlorostyrene, andp-styrenesulfonic acid or an alkali metal salt thereof (sodium salt orpotassium salt, etc.). More preferable are styrene, p-methoxysytrene andp-chlorostyrene. The term “(meth)acrylic acid” refers collectively to“acrylic acid” and “methacrylic acid.”

Examples of compounds represented by the formula (2) and useful for thepresent invention are as follows(R¹Te)₂  (2)wherein R¹ is the same as above.

The groups R¹ is the same as shown above.

Examples of preferred compounds represented by the formula (2) are thosewherein R¹ is C₁-C₄ alkyl or phenyl.

More specific examples of compounds represented by the formula (2) aredimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride,diisopropyl ditelluride, dicyclopropyl ditelluride, di-n-butylditelluride, di-sec-butyl ditelluride, di-tert-butyl ditelluride,dicyclobutyl ditelluride, diphenyl ditelluride,bis(p-methoxyphenyl)ditelluride, bis(p-aminophenyl)ditelluride,bis(p-nitrophenyl)ditelluride, bis(p-cyanophenyl)ditelluride,bis(p-sulfonylphenyl)ditelluride, dinaphthyl ditelluride, dipyridylditelluride, etc. Preferable among these are dimethyl ditelluride,diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride anddiphenyl ditelluride. More preferable are dimethyl ditelluride, diethylditelluride, di-n-propyl ditelluride and di-n-butyl ditelluride.

Such compounds are prepared, for example, by reacting metallic telluriumwith a compound represented by the formula (4).

Metallic tellurium is suspended in a solvent. Examples of solventsusable are dimethylformamide (DMF), tetrahydrofuran (THF) and like polarsolvents, toluene, xylene and like aromatic solvents, hexane and likealiphatic hydrocarbons, dialkyl ethers and like ethers. THF ispreferable among these. The organic solvent is used usually in an amountof 1 to 100 ml, preferably 5 to 10 ml, per gram of metallic telluriumalthough the amount is suitably adjustable.

The compound represented by the formula (4) is slowly added dropwise tothe suspension, followed by stirring. The reaction time is usually 5minutes to 24 hours, preferably 10 minutes to 2 hours, although varyingwith the reaction temperature and pressure. The reaction temperature is−20° C. to 80° C., preferably 15° C. to 40° C., more preferably roomtemperature. The reaction is conducted usually at atmospheric pressure,but an increased or reduced pressure is usable.

Subsequently, water (which may be neutral water such as saline solution,alkali water such as aqueous solution of ammonium chloride, or acidwater such as aqueous solution of hydrochloric acid) is added to thereaction mixture, followed by stirring. Although varying with thereaction temperature or pressure, the reaction time is usually 5 minutesto 24 hours, preferably 10 minutes to 2 hours. The reaction temperatureis −20° C. to 80° C., preferably 15° C. to 40° C., more preferably roomtemperature. The reaction is conducted usually at atmospheric pressure,but an increased or reduced pressure is usable.

Metallic tellurium and the compound of the formula (4) are used in sucha ratio that 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles, of thecompound of the formula (4) is used per mole of metallic tellurium.

After the completion of the reaction, the solvent is concentrated, andthe desired product is isolated from the concentrate and purified.Although the compound can be purified by a suitably selected method,vacuum distillation or reprecipitation purification is usuallydesirable.

Specifically stated, the living radical polymer of the present inventionis produced by the process to be described below.

A vinyl monomer, a living radical polymerization initiator representedby the formula (1) and a compound represented by the formula (2) aremixed together in a container having its inside air replaced by an inertgas. At this time, the initiator represented by the formula (1) and thecompound of the formula (2) may be mixed together by stirring as thefirst step, followed by the second step of adding the vinyl monomer tothe mixture. Examples of inert gases usable at this time are nitrogen,argon, helium, etc., among which argon and nitrogen are preferred.Nitrogen is especially preferred.

Although the vinyl monomer and the initiator represented by the formula(1) are used in amounts which are suitably adjusted depending on themolecular weight and molecular weight distribution of the living radicalpolymer to be obtained, usually 5 to 10,000 moles, preferably 50 to5,000 moles, of the vinyl monomer is used per mole of the initiatorrepresented by the formula (1).

To obtain a preferred mixture of living radical polymerization initiatorof the formula (1) and compound of the formula (2), it is desirable touse an organotellurium compound of the formula (1) wherein R¹ is C₁-C₄alkyl, R² and R³ are each a hydrogen atom or C₁-C₄ alkyl, and R⁴ isaryl, substituted aryl or oxycarbonyl and a compound of the formula (2)wherein R¹ is C₁-C₄ alkyl or phenyl.

The living radical polymerization initiator represented by the formula(1) and the compound represented by the formula (2) are used in theratio of usually 0.1 to 100 moles, preferably 0.5 to 100 moles, morepreferably 1 to 10 moles, especially preferably 1 to 5 moles, of thecompound of the formula (2) per mole of the initiator of the formula(1).

The polymerization reaction is conducted usually in the absence ofsolvent, while an organic solvent generally in use for radicalpolymerization may be used. Examples of solvents usable are benzene,toluene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO),acetone, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethylacetate, trifluoromethylbenzene, etc. Aqueous solvents are also usablewhich include, for example, water, methanol, ethanol, isopropanol,n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol,etc. The amount of the solvent to be used is adjusted suitably. Forexample, 0.01 to 100 ml, preferably 0.05 to 10 ml, more preferably 0.05to 0.5 ml, of the solvent is used per gram of the vinyl monomer.

Next, the mixture is then stirred. The reaction temperature and thereaction time may be adjusted suitably in accordance with the molecularweight or molecular weight distribution of the living radical polymer tobe obtained. The mixture is stirred usually at 60 to 150° C. for 5 to100 hours, preferably at 80 to 120° C. for 10 to 30 hours. The reactionis conducted usually under atmospheric pressure, but may be conducted atincreased pressure or in a vacuum.

After the completion of the reaction, the solvent used and the remainingmonomer are removed in a vacuum to take out the desired polymer, or thedesired product is isolated by re-precipitation using a solvent whereinthe product is insoluble. The reaction mixture can be treated by anymethod insofar as it causes no problem to the desired product.

Different kinds of vinyl monomers are usable in the process of theinvention for preparing a living radical polymer. For example when atleast two kinds of vinyl monomers are reacted at the same time, a randomcopolymer can be obtained. The random copolymer obtained is a polymerwhich comprises the reacted monomers in the original ratio (mole ratio)regardless of the kinds of the monomers. When a random copolymer isobtained by reacting a vinyl monomer A and a vinyl monomer B at the sametime, the copolymer has substantially the same material ratio (moleratio). Further when two kinds of vinyl monomers are reacted insuccession, a block copolymer can be obtained. The block copolymer isprovided by the same order of reacted monomers regardless of the kindsof the monomers. If a vinyl monomer A and a vinyl monomer B are reactedin succession to obtain a block copolymer, the polymer obtained is inthe order of A-B or B-A in conformity with the order of monomersreacted.

The living radical polymerization initiator of the present invention isadapted for excellent control of molecular weights and molecular weightdistributions under very mild conditions.

The living radical polymer to be obtained by the invention is adjustablein molecular weight according to the reaction time, the amount of theliving radical polymerization initiator (organotellurium compound) ofthe formula (1) and the amount of the compound of the formula (2), andcan be 500 to 1,000,000 in number average molecular weight. Theinvention is especially suitable for producing living radical polymershaving a number average molecular weight of 1,000 to 500,000, morepreferably 1,000 to 50,000.

The living radical polymer to be obtained by the invention is controlledto 1.05 to 1.50 in molecular weight distribution (PD=Mw/Mn). Themolecular weight distribution is controllable to a narrower range of1.05 to 1.30, a further narrower range of 1.05 to 1.20, a still narrowerrange of 1.05 to 1.15.

It has been found that the living radical polymer of the presentinvention has a terminal group which is an alkyl, aryl, substitutedaryl, aromatic heterocyclic group, acyl, oxycarbonyl or cyano derivedfrom the organotellurium compound and a growth terminal which is highlyreactive tellurium. Accordingly, the organotellurium compound used forradical polymerization makes it easier to convert the terminal group toother functional group than in the case of the living radical polymerobtained by conventional living radical polymerization. The livingradical polymer obtained according to the invention is therefore usableas a macro living radical polymerization initiator (macroinitiator).

A-B diblock copolymers such as methyl methacrylate-styrene and B-Adiblock copolymers such as styrene-methyl methacrylate can be obtainedusing a macro living radical polymerization initiator of the invention.A-B-A triblock copolymers such as methyl methacrylate-styrene-methylmethacrylate and A-B-C triblock copolymers such as methylmethacrylate-styrene-butyl acrylate are also available. This isattributable to the fact that the vinyl monomers of various differenttypes are controllable by the living radical polymerization initiatorand the ditellurium compound of the invention, and also to the fact thathighly reactive tellurium is present at the growth terminal of theliving radical polymer obtained with use of the living radicalpolymerization initiator.

Stated more specifically, block copolymers are prepared by the processesto be described below.

For preparing A-B diblock copolymers such as methyl methacrylate-styrenecopolymer, methyl methacrylate, a living radical polymerizationinitiator represented by the formula (1) and a compound represented bythe formula (2) are mixed together first as in the process describedabove for preparing a living radical polymer to obtain poly(methylmethacrylate), and subsequently mixing styrene with the polymer toobtain methyl methacrylate-styrene copolymer.

A-B-A triblock copolymers and A-B-C triblock copolymers can be produced,for example, by preparing an A-B diblock copolymer by the above processand thereafter mixing a vinyl monomer (A) or vinyl monomer (C) with thecopolymer to obtain the A-B-A or A-B-C triblock copolymer.

In producing the diblock copolymer according to the invention, thecompound of the formula (1) and the compound of the formula (2) can beused when a homopolymer is prepared from the first monomer and/or whenthe diblock copolymer is subsequently prepared.

Further in producing the triblock copolymer according to the inventionthe compound of the formula (1) and the compound of the formula (2) canbe used at least once when a homopolymer is prepared from the firstmonomer, or when a diblock copolymer is subsequently prepared, or whenthe triblock copolymer is subsequently prepared.

The preparation of each block may be followed directly by the subsequentreaction for the next block, or the subsequent reaction for the nextblock may be initiated after the purification of the product resultingfrom the completion of the first reaction. The block copolymer can beisolated by a usual method.

BEST MODE OF CARRYING OUT THE INVENTION

The present invention will be described below in detail with referenceto Examples, but is not limited thereto in any way. In Examples andComparative Examples, properties were determined by the followingmethods.

(1) Identification of Organotellurium Compounds and Living RadicalPolymers

The organotellurium compound was identified based on the results of¹H-NMR, ¹³C-NMR, IR and MS analyses. The molecular weight and molecularweight distribution of the living radical polymer were determined usingGPC (gel permeation chromatography). The measuring instruments used areas follows.

¹H-NMR: Varian Gemini 2000 (300 MHz for ¹H), JEOL JNM-A400 (400 MHz for¹H) ¹³C-NMR: Varian Gemini 2000, JEOL JNM-A400 IR: Shimadzu FTIR-8200(cm⁻¹) MS (HRMS): JEOL JMS-300

Molecular weight and molecular weight distribution: liquidchromatography Shimadzu LC-10 (column: Shodex K-804L+K-805L, polystyrenestandard: TOSOH TSK Standard, polymethyl methacrylate standard: ShodexStandard M-75)

PREPARATION EXAMPLE 1 Preparation of (1-methyltellanyl-ethyl)benzene

A 6.38 g quantity (50 mmoles) of metallic tellurium [product of Aldrich,brand name: Tellurium (−40 mesh)] was suspended in 50 ml of THF, and52.9 ml (1.04 M diethyl ether solution, 55 mmoles) of methyllithium(product of Kanto Chemical Co., Ltd., diethyl ether solution) was slowlyadded dropwise to the suspension at room temperature (for 10 minutes).The reaction mixture was stirred until the metallic telluriumdisappeared completely (for 20 minutes). To the reaction mixture wasadded 11.0 g (60 mmoles) of (1-bromoethyl)benzene at room temperature,followed by stirring for 2 hours. After the completion of reaction, thesolvent was concentrated in a vacuum, followed by vacuum distillation togive 8.66 g of yellow oil (70% in yield).

IR, HRMS, ¹H-NMR and ¹³C-NMR analyses indicated that the product was(1-methyltellanyl-ethyl)benzene.

IR (neat, cm⁻¹) 1599, 1493, 1451, 1375, 1219, 1140, 830, 760, 696, 577HRMS (EI) m/z: Calcd for C₉H₁₂Te(M)⁺, 250.0001; Found 250.0001. ¹H-NMR(300 MHz, CDCl₃) 1.78 (s, 3H, TeCH₃), 1.90 (d, J=7.2 Hz, 3H), 4.57 (q,J=7.2 Hz, 1H, CHTe), 7.08-7.32 (m, 5H) ¹³C-NMR (75 MHz, CDCl₃) −18.94,18.30, 23.89, 126.17, 126.80, 128.30, 145.79

PREPARATION EXAMPLE 2 Preparation ofethyl-2-methyl-2-methyltellanyl-propionate

The same procedure as in Preparation Example 1 was performed with theexception of using 10.7 g (55 mmoles) of ethyl-2-bromo-isobutyrate inplace of (1-bromoethyl)benzene to obtain 6.53 g (51% in yield) of yellowoil.

IR, HRMS, ¹H-NMR and ¹³C-NMR analyses indicated that the product wasethyl-2-methyl-2-methyltellanyl-propionate. IR (neat, cm⁻¹) 1700, 1466,1385, 1269, 1146, 1111, 1028 HRMS (EI) m/z: Calcd for C₇H₁₄O₂Te(M)⁺,260.0056; Found 260.0053. ¹H-NMR (300 MHz, CDCl₃) 1.27 (t, J=6.9 Hz,3H), 1.74 (s, 6H), 2.15 (s, 3H, TeCH₃), 4.16 (q, J=7.2 Hz, 2H) ¹³C-NMR(75 MHz, CDCl₃)-17.38, 13.89, 23.42, 27.93, 60.80, 176.75

PREPARATION EXAMPLE 3 Dimethyl Ditelluride

A 3.19 g quantity (25 mmoles) of metallic tellurium (the same as above)was suspended in 25 ml of THF, and 25 ml (28.5 mmoles) of methyllithium(the same as above) was added slowly to the suspension at 0° C. (over aperiod of 10 minutes). The reaction mixture was stirred until themetallic tellurium disappeared completely (for 10 minutes). To theresulting reaction mixture was added 20 ml of a solution of ammoniumchloride at room temperature, followed by stirring for 1 hour. Theorganic layer was separated off, and the aqueous layer was subjected toextraction with diethyl ether 3 times. The organic layers werecollected, dried over anhydrous sodium sulfate and concentrated in avacuum, affording 2.69 g (9.4 mmoles, yield 75%) of blackish purple oil.

The product was found to be dimethyl ditelluride by MS (HRMS) and¹H-NMR.

HRMS (EI) m/z: Calcd for C₂H₆Te₂(M)⁺, 289.8594; Found 289.8593. ¹H-NMR(300 MHz, CDCl₃) 2.67 (s, 6H)

PREPARATION EXAMPLE 4 Diphenyl Ditelluride

A 3.19 g quantity (25 mmoles) of metallic tellurium (the same as above)was suspended in 25 ml of THF, and 15.8 ml (28.5 mmoles) ofphenyllithium [product of Aldrich, 1.8M-cyclohexane/ether (70:30)solution] was added slowly to the suspension at 0° C. (over a period of10 minutes). The reaction mixture was stirred until the metallictellurium disappeared completely (for 10 minutes). To the resultingreaction mixture was added 20 ml of a solution of ammonium chloride atroom temperature, followed by stirring for 1 hour. The organic layer wasseparated off, and the aqueous layer was subjected to extraction withdiethyl ether 3 times. The organic layers were collected, dried overanhydrous sodium sulfate and concentrated in a vacuum, affording 3.48 g(8.5 mmoles, yield 68%) of blackish purple oil.

The product was found to be diphenyl ditelluride by MS (HRMS) and¹H-NMR.

EXAMPLES 1 TO 4 Preparation of poly(methyl methacrylate)

Along with 24.8 mg (0.10 mmole) of the (1-methyltellanyl-ethyl)benzeneprepared in Preparation Example 1, methyl methacrylate [stabilized withhydroquinone (HQ)] and a solution of the dimethyl ditelluride preparedin Preparation Example 3 were placed in the ratio listed in Table 1 intoa glove box with the inside air replaced by nitrogen, followed bystirring. After the completion of the reaction, the reaction mixture wasdissolved in 5 ml of chloroform, and the solution was then poured into250 ml of hexane which was being stirred. The resulting polymerprecipitate was collected by suction filtration and dried to obtainpoly(methyl methacrylate).

Table 1 shows the result of GPC analysis [with reference to themolecular weight of an authentic sample of poly(methyl methacrylate)].

TABLE 1 methyl dimethyl reaction yield Ex. methacrylate ditelluridecondition (%) Mn PD 1 1.01 g 28.5 mg 80° C. 92 9700 1.18 (10 mmol) (0.10mmol) 13 h 2 2.02 g 28.5 mg 80° C. 83 16100 1.14 (20 mmol) (0.10 mmol)13 h 3 5.05 g 57.0 mg 80° C. 79 36300 1.18 (50 mmol) (0.20 mmol) 18 h 410.10 g 57.0 mg 80° C. 83 79400 1.14 (100 mmol) (0.20 mmol) 24 h

COMPARATIVE EXAMPLE 1 Preparation of poly(methyl methacrylate)

Poly(methyl methacrylate) was prepared in the same manner as in Example1 except that no dimethyl ditelluride was used (67% in yield).

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 8100 and PD=1.77.

A comparison between Example 1 and Comparative Example 1 indicates thatwhen dimethyl telluride was used as a compound represented by theformula (2), a living radical polymer of narrower molecular weightdistribution (PD value closer to 1) is obtained.

EXAMPLE 5 Preparation of poly(methyl methacrylate)

A 25.8 mg quantity (0.10 mmole) of theethyl-2-methyl-2-methyltellanyl-propionate prepared in PreparationExample 2, 1.01 g (10 mmoles) of methyl methacrylate and a solution of28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared in PreparationExample 3 were stirred at 80° C. for 13 hours within a glove box havingits inside air replaced by nitrogen. After the completion of thereaction, the reaction mixture was dissolved in 5 ml of chloroform, andthe solution was thereafter poured into 250 ml of hexane being stirred.The resulting polymer precipitate was collected by suction filtrationand dried, affording 0.85 g (yield 84%) of poly(methyl methacrylate).

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 8200 and PD=1.16.

EXAMPLE 6 Preparation of poly(ethyl methacrylate)

A 25.8 mg quantity (0.10 mmole) of theethyl-2-methyl-2-methyltellanyl-propionate prepared in PreparationExample 2, 1.14 g (10 mmoles) of ethyl methacrylate (stabilized with HQ)and a solution of 28.5 mg (0.10 mmole) of the dimethyl ditellurideprepared in Preparation Example 3 were stirred at 105° C. for 2 hourswithin a glove box having its inside air replaced by nitrogen. After thecompletion of the reaction, the reaction mixture was dissolved in 5 mlof chloroform, and the solution was thereafter poured into 250 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording 1.11 g (yield 97%) ofpoly(ethylmethacrylate).

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 10600 and PD=1.12.

EXAMPLE 7 Preparation of poly(2-hydroxyethyl methacrylate)

In 1 ml of N,N-dimethylformamide (DMF) were dissolved 25.8 mg (0.10mmole) of the ethyl-2-methyl-2-methyltellanyl-propionate prepared inPreparation Example 2, 1.30 g (10 mmoles) of 2-hydroxyethyl methacrylate[stabilized with hydroquinone methyl ether (MEHQ)] and 28.5 mg (0.10mmole) of the dimethyl ditelluride prepared in Preparation Example 3 ina glove box having its inside air replaced by nitrogen. The solution wasstirred at 80° C. for 8 hours. After the completion of the reaction, thesolvent was removed by distillation in a vacuum, affording 1.26 g (yield97%) of poly(2-hydroxyethyl methacrylate).

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 22300 and PD=1.27.

EXAMPLE 8 Preparation of Polystyrene

A 24.8 mg quantity (0.10 mmole) of the (1-methyltellanyl-ethyl)benzeneprepared in Preparation Example 1, 1.04 g (10 mmoles) of styrene and asolution of 28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared inPreparation Example 3 were stirred at 120° C. for 14 hours within aglove box having its inside air replaced by nitrogen. After thecompletion of the reaction, the reaction mixture was dissolved in 5 mlof chloroform, and the solution was thereafter poured into 250 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording 1.01 g (yield 97%) ofpolystyrene.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 9000 and PD=1.18.

EXAMPLE 9 Preparation of Polystyrene

A 24.8 mg quantity (0.10 mmole) of the (1-methyltellanyl-ethyl)benzeneprepared in Preparation Example 1, 1.04 g (10 mmoles) of styrene and asolution of 40.9 mg (0.10 mmole) of the diphenyl ditelluride prepared inPreparation Example 4 were stirred at 120° C. for 14 hours within aglove box having its inside air replaced by nitrogen. After thecompletion of the reaction, the reaction mixture was dissolved in 5 mlof chloroform, and the solution was thereafter poured into 250 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording 0.99 g (yield 95%) ofpolystyrene.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 9200 and PD=1.13.

EXAMPLE 10 Preparation of poly(methyl methacrylate-b-styrene) diblockpolymer

A 1.01 g quantity (10 mmoles) of methyl methacrylate, 24.8 mg (0.10mmole) of the (1-methyltellanyl-ethyl)benzene prepared in PreparationExample 1 and 28.5 mg (0.10 mmole) of the dimethyl ditelluride preparedin Preparation Example 3 were reacted at 100° C. for 24 hours in a glovebox having its inside air replaced by nitrogen. After the completion ofthe reaction, the reaction mixture was dissolved in 5 ml ofdeuterochloroform, and the solution was thereafter poured into 300 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording 0.765 g (yield 86%) ofpoly(methyl methacrylate).

GPC analysis revealed Mn 8500 and PD=1.12.

Next, 425 mg (0.05 mmole) of the poly(methyl methacrylate) (used as amacroinitiator) obtained above and 520 mg (5 mmoles) of styrene werereacted at 100° C. for 24 hours. After the completion of the reaction,the reaction mixture was dissolved in 5 ml of chloroform, and thesolution was thereafter poured into 300 ml of hexane being stirred. Theresulting polymer precipitate was collected by suction filtration anddried, affording 0.5353 g (yield 57%) of poly(methylmethacrylate-b-styrene) diblock polymer. GPC analysis revealed Mn 18700and PD=1.18.

PREPARATION EXAMPLE 5 Preparation of1-chloro-4-(1-methyltellanyl-ethyl)benzene

A 4.08 g quantity (32 mmoles) of metallic tellurium (the same as above)was suspended in 50 ml of THF, and 29.2 ml (35 mmoles of 1.20M diethylether solution) of methyllithium was slowly added dropwise to thesuspension at 0° C. (over a period of 10 minutes). The reaction mixturewas stirred until the metallic tellurium disappeared completely (for 15minutes). To the reaction mixture was added 7.68 g (35 mmoles) of1-(1-bromoethyl)-4-chlorobenzene at 0° C., followed by stirring at roomtemperature for 1.5 hours. After the completion of the reaction, thesolvent was concentrated in a vacuum, and the concentrate was thendistilled in a vacuum, giving 3.59 g (yield 40%) of orange oil.

IR, HRMS, ¹H-NMR and ¹³C-NMR indicated that the product was1-chloro-4-(1-methyltellanyl-ethyl)benzene.

IR (neat, cm⁻¹) 1891, 1686, 1489, 1408, 1096, 828 HRMS (EI) m/z: Calcdfor C₉H₁₁ClTe(M)⁺, 283.9.612; Found 283.9601 ¹H-NMR (300 MHz, CDCl₃)1.81 (s, 3H), 1.88 (d, J=7.2 Hz, 3H), 4.54 (q, J=7.2 Hz, H), 7.23 (s,5H) ¹³C-NMR (100 MHz, CDCl₃)-18.80, 17.18, 23.81, 128.08, 128.39,131.51, 144.45.

PREPARATION EXAMPLE 6 Preparation of1-(1-methyltellanyl-ethyl)-4-trifluoromethylbenzene

A 5.74 g quantity (45 mmoles) of metallic tellurium (the same as above)was suspended in 60 ml of THF, and 45.5 ml (50 mmoles of 1.10M diethylether solution) of methyllithium was slowly added dropwise to thesuspension at 0° C. (over a period of 10 minutes). The reaction mixturewas stirred until the metallic tellurium disappeared completely (for 20minutes). To the reaction mixture was added 11.4 g (45 mmoles) of1-(1-bromoethyl)-4-trifluoromethylbenzene at 0° C., followed by stirringat room temperature for 1.5 hours. After the completion of the reaction,the solvent was concentrated in a vacuum, and the concentrate was thendistilled in a vacuum, giving 2.40 g (yield 17%) of yellow oil.

IR, HRMS, ¹H-NMR and ¹³C-NMR indicated that the product was1-(1-methyltellanyl-ethyl)-4-trifluoromethylbenzene.

IR (neat, cm⁻¹) 1918, 1698, 1617, 1416, 1325, 841 HRMS (EI) m/z: Calcdfor C₁₀H₁₁F₃Te(M)⁺, 317.9875; Found 317.9877 ¹H-NMR (300 MHz, CDCl₃)1.84 (s, 3H), 1.92 (d, J=6.9, 3H), 4.59 (q, J=7.3 Hz, 1H), 7.39 (d,J=8.1 Hz, 2H), 7.53 (d, J=8.4 Hz, 2H) ¹³C-NMR (100 MHz, CDCl₃) −18.72,17.17, 23.51, 122.83, 125.55 (q, J_(C-F)=3.8 Hz), 127.04, 128.29 (q,J_(C-F)=32.2 Hz), 150.18 (q, J_(C-F)=1.3 Hz).

PREPARATION EXAMPLE 7 Preparation of1-(1-methyltellanyl-ethyl)-3,5-bis-trifluoromethylbenzene

A 4.59 g quantity (36 mmoles) of metallic tellurium (the same as above)was suspended in 60 ml of THF, and 36.7 ml (40 mmoles of 1.20M diethylether solution) of methyllithium was slowly added dropwise to thesuspension at 0° C. (over a period of 10 minutes). The reaction mixturewas stirred until the metallic tellurium disappeared completely (for 10minutes). To the reaction mixture was added 12.8 g (40 mmoles) of1-(1-bromoethyl)-3,5-bis-trifluoromethyl-benzene at 0° C., followed bystirring at room temperature for 2 hours. After the completion of thereaction, the solvent was concentrated in a vacuum, and the concentratewas then distilled in a vacuum, giving 4.63 g (yield 30%) of orange oil.

IR, HRMS, ¹H-NMR and ¹³C-NMR indicated that the product was1-(1-methyltellanyl-ethyl)-3,5-bis-trifluoromethylbenzene.

IR (neat, cm⁻¹) 1620, 1468, 1375, 1279, 1175, 893 HRMS (EI) m/z: Calcdfor C₁₁H₁₀F₆Te(M)⁺, 385, 9749; Found 385.9749 ¹H-NMR (300 MHz, CDCl₃)1.87 (s, 3H), 1.95 (d, J=7.2, 3H), 4.62 (q, J=7.3 Hz, 1H), 7.68 (s, 1H),7.70 (s, 2H) ¹³C-NMR (100 MHz, CDCl₃)-18.49, 16.14, 23.33, 120.2 (hept,J_(C-F)=3.8 Hz), 121.94, 124.65, 126.75, 131.64 (q, J_(C-F)=32.9 Hz),148.96.

PREPARATION EXAMPLE 8 Preparation of1,2,3,4,5-pentafluoro-6-(1-methyltellanyl-ethyl)benzene

A 5.74 g quantity (45 mmoles) of metallic tellurium (the same as above)was suspended in 60 ml of THF, and 42.0 ml (50 mmoles of 1.20M diethylether solution) of methyllithium was slowly added dropwise to thesuspension at 0° C. (over a period of 10 minutes). The reaction mixturewas stirred until the metallic tellurium disappeared completely (for 30minutes). To the reaction mixture was added 12.4 g (45 mmoles) of1,2,3,4,5-pentafluoro-6-(1-bromoethyl)benzene at 0° C., followed bystirring at room temperature for 2 hours. After the completion of thereaction, the solvent was concentrated in a vacuum, and the concentratewas then distilled in a vacuum, giving 2.86 g (yield 19%) of orange oil.

IR, HRMS, ¹H-NMR and ¹³C-NMR indicated that the product was1,2,3,4,5-pentafluoro-6-(1-methyltellanyl-ethyl)benzene.

IR (neat, cm⁻¹) 1653, 1522, 1499, 1144, 1075, 1048, 984, 903 HRMS (EI)m/z: Calcd for C₉H₇F₅Te(M)⁺, 339.9530; Found 339.9535 ¹H-NMR (300 MHz,CDCl₃) 1.93 (d, J=7.2 Hz, 3H), 2.05 (s, 3H), 4.65 (q, J=7.5 Hz, 1H)¹³C-NMR (100 MHz, CDCl₃)-19.07, 2.01, 22.38, 120.79-121.14 (m), 137.59(dddd, J_(C-F)=261 Hz), 139.52 (dtt, J_(C-F)=249 Hz), 143.38 (dm,J_(C-F)=248 Hz)

PREPARATION EXAMPLE 9 Preparation of1-methoxy-4-(1-methyltellanyl-ethyl)benzene

A 7.66 g quantity (60 mmoles) of metallic tellurium (the same as above)was suspended in 50 ml of THF, and 55.0 ml (66 mmoles of 1.20M diethylether solution) of methyllithium was slowly added dropwise to thesuspension at 0° C. (over a period of 10 minutes). The reaction mixturewas stirred until the metallic tellurium disappeared completely (for 30minutes). To the reaction mixture was added 12.9 g (60 mmoles) of1-(1-bromoethyl)-4-methoxybenzene at 0° C., followed by stirring at roomtemperature for 1.5 hours. After the completion of the reaction, thesolvent was concentrated in a vacuum, and the concentrate was thendistilled in a vacuum, giving 10.8 g (yield 40%) of orange oil.

IR, HRMS, ¹H-NMR and ¹³C-NMR indicated that the product was1-methoxy-4-(1-methyltellanyl-ethyl)benzene.

IR (neat, cm⁻¹) 1609, 1509, 1248, 1177, 1040, 830 HRMS (EI) m/z: Calcdfor C₁₀H₁₄OTe(M)⁺, 281.0107; Found 281.0106 ¹H-NMR (300 MHz, CDCl₃) 1.78(s, 3H), 1.89 (d, J=7.2 Hz, 3H), 4.58 (q, J=7.3 Hz, 1H), 6.83 (d, J=8.4Hz, 2H), 7.23 (d, J=9.0 Hz, 2H) ¹³C-NMR (100 MHz, CDCl₃)-18.98, 17.94,24.30, 55.23, 113.70, 127.86, 137.95, 157.84.

PREPARATION EXAMPLE 10 Preparation ofethyl-2-methyl-2-n-butyltellanyl-propionate

A 6.38 g quantity (50 mmoles) of metallic tellurium (the same as above)was suspended in 50 ml of THF, and 34.4 ml (55 mmoles) of n-butyllithium(product of Aldrich, 1.6M hexane solution) was slowly added dropwise tothe suspension at room temperature (over a period of 10 minutes). Thereaction mixture was stirred until the metallic tellurium disappearedcompletely (for 20 minutes). To the reaction mixture was added 10.7 g(55 mmoles) of ethyl-2-bromo-isobutyrate at room temperature, followedby stirring for 2 hours. After the completion of the reaction, thesolvent was concentrated in a vacuum, and the concentrate wassubsequently distilled in a vacuum, giving 8.98 g (yield 59.5%) ofyellow oil.

¹H-NMR indicated that the product wasethyl-2-methyl-2-n-butyltellanyl-propionate.

¹H-NMR (300 MHz, CDCl₃) 0.93 (t, J=7.5 Hz, 3H), 1.25 (t, J=7.2 Hz, 3H),1.37 (m, 2H), 1.74 (s, 6H), 1.76 (m, 2H), 2.90 (t, J=7.5 Hz, 2H, CH₂Te),4.14 (q, J=7.2 Hz, 2H)

PREPARATION EXAMPLE 11 Preparation of di-n-butyl Ditelluride

A 3.19 g quantity (25 mmoles) of metallic tellurium (the same as above)was suspended in 25 ml of THF, and 17.2 ml (27.5 mmoles) ofn-butyllithium (product of Aldrich, 1.6M hexane solution) was addedslowly to the suspension at 0° C. (over a period of 10 minutes). Thereaction mixture was stirred until the metallic tellurium disappearedcompletely (for 10 minutes). To the resulting reaction mixture was added20 ml of a solution of ammonium chloride at room temperature, followedby stirring for 1 hour. The organic layer was separated off, and theaqueous layer was subjected to extraction with diethyl ether 3 times.The organic layers were collected, dried over Glauber's salt andconcentrated in a vacuum, affording 4.41 g (11.93 mmoles, yield 95%) ofblackish purple oil.

The product was found to be di-n-butyl ditelluride by ¹H-NMR. ¹H-NMR(300 MHz, CDCl₃) 0.93 (t, J=7.3 Hz, 3H), 1.39 (m, 2H), 1.71 (m, 2H),3.11 (t, J=7.6, 2H, CH₂Te)

EXAMPLE 11 Preparation of poly(methyl methacrylate)

A 28.4 mg quantity (0.10 mmole) of the1-chloro-4-(1-methyltellanyl-ethyl)benzene prepared in PreparationExample 5, 1.01 g (10 mmoles) of methyl methacrylate and a solution of28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared in PreparationExample 3 were stirred at 80° C. for 13 hours within a glove box havingits inside air replaced by nitrogen. After the completion of thereaction, the reaction mixture was dissolved in 5 ml of chloroform, andthe solution was thereafter poured into 250 ml of hexane being stirred.The resulting polymer precipitate was collected by suction filtrationand dried, affording poly(methyl methacrylate) in a yield of 71%.

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 6000 and PD=1.12.

EXAMPLE 12 Preparation of poly(methyl methacrylate)

A 31.8 mg quantity (0.10 mmole) of the1-(1-methyltellanyl-ethyl)-4-trifluoromethylbenzene prepared inPreparation Example 6, 1.01 g (10 mmoles) of methyl methacrylate and asolution of 28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared inPreparation Example 3 were stirred at 80° C. for 13 hours within a glovebox having its inside air replaced by nitrogen. After the completion ofthe reaction, the reaction mixture was dissolved in 5 ml of chloroform,and the solution was thereafter poured into 250 ml of hexane beingstirred. The resulting polymer precipitate was collected by suctionfiltration and dried, affording poly(methyl methacrylate) in a yield of93%.

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 6800 and PD=1.16.

EXAMPLE 13 Preparation of poly(methyl methacrylate)

A 38.6 mg quantity (0.10 mmole) of the1-(1-methyltellanyl-ethyl)-3,5-bis-trifluoromethylbenzene prepared inPreparation Example 7, 1.01 g (10 mmoles) of methyl methacrylate and asolution of 28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared inPreparation Example 3 were stirred at 80° C. for 13 hours within a glovebox having its inside air replaced by nitrogen. After the completion ofthe reaction, the reaction mixture was dissolved in 5 ml of chloroform,and the solution was thereafter poured into 250 ml of hexane beingstirred. The resulting polymer precipitate was collected by suctionfiltration and dried, affording poly(methyl methacrylate) in a yield of69%.

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 6600 and PD=1.11.

EXAMPLE 14 Preparation of poly(methyl methacrylate)

A 34.0 mg quantity (0.10 mmole) of the1,2,3,4,5-pentafluoro-6-(1-methyltellanyl-ethyl)benzene prepared inPreparation Example 8, 1.01 g (10 mmoles) of methyl methacrylate and asolution of 28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared inPreparation Example 3 were stirred at 80° C. for 13 hours within a glovebox having its inside air replaced by nitrogen. After the completion ofthe reaction, the reaction mixture was dissolved in 5 ml of chloroform,and the solution was thereafter poured into 250 ml of hexane beingstirred. The resulting polymer precipitate was collected by suctionfiltration and dried, affording poly(methyl methacrylate) in a yield of44%.

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 5200 and PD=1.25.

EXAMPLE 15 Preparation of poly(methyl methacrylate)

A 28.1 mg quantity (0.10 mmole) of the1-methoxy-4-(1-methyltellanyl-ethyl)benzene prepared in PreparationExample 9, 1.01 g (10 mmoles) of methyl methacrylate and a solution of28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared in PreparationExample 3 were stirred at 80° C. for 13 hours within a glove box havingits inside air replaced by nitrogen. After the completion of thereaction, the reaction mixture was dissolved in 5 ml of chloroform, andthe solution was thereafter poured into 250 ml of hexane being stirred.The resulting polymer precipitate was collected by suction filtrationand dried, affording poly(methyl methacrylate) in a yield of 83%.

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 6500 and PD=1.17.

EXAMPLE 16 Preparation of Polystyrene

A 24.8 mg quantity (0.10 mmole) of the (1-methyltellanyl-ethyl)benzeneprepared in Preparation Example 1, 1.04 g (10 mmoles) of styrene and asolution of 28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared inPreparation Example 3 were stirred at 100° C. for 20 hours within aglove box having its inside air replaced by nitrogen. After thecompletion of the reaction, the reaction mixture was dissolved in 5 mlof chloroform, and the solution was thereafter poured into 250 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording polystyrene in a yield of 74%.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 6500 and PD=1.10.

EXAMPLE 17 Preparation of Polystyrene

A 28.4 mg quantity (0.10 mmole) of the1-chloro-4-(1-methyltellanyl-ethyl)benzene prepared in PreparationExample 5, 1.04 g (10 mmoles) of styrene and a solution of 28.5 mg (0.10mmole) of the dimethyl ditelluride prepared in Preparation Example 3were stirred at 100° C. for 20 hours within a glove box having itsinside air replaced by nitrogen. After the completion of the reaction,the reaction mixture was dissolved in 5 ml of chloroform, and thesolution was thereafter poured into 250 ml of hexane being stirred. Theresulting polymer precipitate was collected by suction filtration anddried, affording polystyrene in a yield of 76%.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 8100 and PD=1.14.

EXAMPLE 18 Preparation of poly(p-chlorostyrene)

A 24.8 mg quantity (0.10 mmole) of the (1-methyltellanyl-ethyl)benzeneprepared in Preparation Example 1, 1.39 g (10 mmoles) of p-chlorostyreneand a solution of 28.5 mg (0.10 mmole) of the dimethyl ditellurideprepared in Preparation Example 3 were stirred at 100° C. for 17 hourswithin a glove box having its inside air replaced by nitrogen. After thecompletion of the reaction, the reaction mixture was dissolved in 5 mlof chloroform, and the solution was thereafter poured into 250 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording poly(p-chlorostyrene) in a yieldof 92%.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 6400 and PD=1.14.

EXAMPLE 19 Preparation of poly(p-chlorostyrene)

A 28.4 mg quantity (0.10 mmole) of the1-chloro-4-(1-methyltellanyl-ethyl)benzene prepared in PreparationExample 5, 1.39 g (10 mmoles) of p-chlorostyrene and a solution of 28.5mg (0.10 mmole) of the dimethyl ditelluride prepared in PreparationExample 3 were stirred at 100° C. for 10 hours within a glove box havingits inside air replaced by nitrogen. After the completion of thereaction, the reaction mixture was dissolved in 5 ml of chloroform, andthe solution was thereafter poured into 250 ml of hexane being stirred.The resulting polymer precipitate was collected by suction filtrationand dried, affording poly(p-chlorostyrene) in a yield of 77%.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 7300 and PD=1.07.

EXAMPLE 20 Preparation of poly(methyl vinyl ketone)

A 25.8 mg quantity (0.10 mmole) of theethyl-2-methyl-2-methyltellanyl-propionate prepared in PreparationExample 2, 0.70 g (10 mmoles) of methyl vinyl ketone and a solution of28.5 mg (0.10 mmole) of the dimethyl ditelluride prepared in PreparationExample 3 were stirred at 80° C. for 48 hours within a glove box havingits inside air replaced by nitrogen. After the completion of thereaction, the reaction mixture was dissolved in 5 ml of chloroform, andthe solution was thereafter poured into 250 ml of hexane being stirred.The resulting polymer precipitate was collected by suction filtrationand dried, affording poly(methyl vinyl ketone) in a yield of 21%.

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 7800 and PD=1.25.

EXAMPLE 21 Preparation of poly(methacrvlonitrile)

A solution of 25.8 mg quantity (0.10 mmole) of theethyl-2-methyl-2-methyltellanyl-propionate prepared in PreparationExample 2, 671 mg (10 mmoles) of methacrvlonitrile, 28.5 mg (0.10 mmole)of the dimethyl ditelluride prepared in Preparation Example 3 and 0.5 mlof dimethylformamide (DMF) were stirred at 80° C. for 48 hours within aglove box having its inside air replaced by nitrogen. After thecompletion of the reaction, the reaction mixture was dissolved in 5 mlof chloroform, and the solution was thereafter poured into 250 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording poly(methacrvlonitrile) in ayield of 48%.

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 5900 and PD=1.09.

EXAMPLE 22 Preparation of poly(N-methyl methacrylamide)

A solution of 25.8 mg quantity (0.10 mmole) of theethyl-2-methyl-2-methyltellanyl-propionate prepared in PreparationExample 2, 0.99 g (10 mmoles) of N-methyl methacrylamide, 28.5 mg (0.10mmole) of the dimethyl ditelluride prepared in Preparation Example 3 and0.5 ml of dimethylformamide (DMF) were stirred at 80° C. for 48 hourswithin a glove box having its inside air replaced by nitrogen. After thecompletion of the reaction, the reaction mixture was dissolved in 5 mlof chloroform, and the solution was thereafter poured into 250 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording poly(N-methyl methacrylamide) ina yield of 78%.

GPC analysis [with reference to the molecular weight of an authenticsample of poly(methyl methacrylate)] revealed Mn 9300 and PD=1.18.

EXAMPLES 23 TO 25 Preparation of poly(methyl methacrylate)

Methyl methacrylate [stabilized with hydroquinone (HQ)] and a solutionof the dimethyl ditelluride prepared in Preparation Example 3 werestirred in the ratio listed in Table 2 along with 25.8 mg (0.10 mmole)of the ethyl-2-methyl-2-methyltellanyl-propionate prepared inPreparation Example 2 in a glove box having its inside air replaced bynitrogen. After the completion of the reaction, a portion of thereaction mixture was dissolved in 5 ml of chloroform, and the solutionwas thereafter poured into 250 ml of hexane being stirred. The resultingpolymer precipitate was collected by suction filtration and dried,affording poly(methyl methacrylate).

Table 2 shows the result of GPC analysis [with reference to themolecular weight of an authentic sample of poly(methyl methacrylate)].

TABLE 2 methyl dimethyl reaction yield Ex. methacrylate ditelluridecondition (%) Mn PD 23 10.1 g 57.0 mg 80° C., 57.8 47000 1.19 (100 mmol)(0.2 mmol) 10 h 24 50.5 g 142.5 mg 80° C., 86.0 278000 1.44 (500 mmol)(0.5 mmol) 10 h 25 87.9 g 285 mg 80° C., 70.0 514000 1.48 (870 mmol)(1.0 mmol) 36 h

EXAMPLE 26 Random Copolymer of Styrene and Methyl Methacrylate

A 45.27 mg quantity (0.15 mmole) of theethyl-2-methyl-2-n-butyltellanyl-propionate prepared in PreparationExample 10, 1.04 g (10 mmoles) of styrene, 0.5 g (5 mmoles) of methylmethacrylate and a solution of 55.5 mg (0.15 mmole) of the di-n-butylditelluride prepared in Preparation Example 11 were stirred at 80° C.for 30 hours within a glove box having its inside air replaced bynitrogen. After the completion of the reaction, the reaction mixture wasdissolved in 5 ml of chloroform, and the solution was thereafter pouredinto 250 ml of hexane being stirred. The resulting polymer precipitatewas collected by suction filtration and dried, affording a randomcopolymer of styrene and methyl methacrylate in a yield of 88%.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 9900 and PD=1.19.

EXAMPLE 27 Random Copolymer of Styrene and Methyl Methacrylate

A 45.27 mg quantity (0.15 mmole) of theethyl-2-methyl-2-n-butyltellanyl-propionate prepared in PreparationExample 10, 0.78 g (7.5 mmoles) of styrene, 0.76 g (7.5 mmoles) ofmethyl methacrylate and a solution of 55.5 mg (0.15 mmole) of thedi-n-butyl ditelluride prepared in Preparation Example 11 were stirredat 80° C. for 30 hours within a glove box having its inside air replacedby nitrogen. After the completion of the reaction, the reaction mixturewas dissolved in 5 ml of chloroform, and the solution was thereafterpoured into 250 ml of hexane being stirred. The resulting polymerprecipitate was collected by suction filtration and dried, affording arandom copolymer of styrene and methyl methacrylate in a yield of 92%.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 10500 and PD=1.23.

EXAMPLE 28 Random Copolymer of Styrene and Methyl Methacrylate

A 45.27 mg quantity (0.15 mmole) of theethyl-2-methyl-2-n-butyltellanyl-propionate prepared in PreparationExample 10, 0.52 g (5 mmoles) of styrene, 1.01 g (10 mmoles) of methylmethacrylate and a solution of 55.5 mg (0.15 mmole) of the di-n-butylditelluride prepared in Preparation Example 11 were stirred at 80° C.for 30 hours within a glove box having its inside air replaced bynitrogen. After the completion of the reaction, the reaction mixture wasdissolved in 5 ml of chloroform, and the solution was thereafter pouredinto 250 ml of hexane being stirred. The resulting polymer precipitatewas collected by suction filtration and dried, affording a randomcopolymer of styrene and methyl methacrylate in a yield of 85%.

GPC analysis (with reference to the molecular weight of an authenticsample of polystyrene) revealed Mn 16000 and PD=1.23.

EXPERIMENTAL EXAMPLE 1 Elemental Analysis of C, H, N

The random copolymers of styrene and methyl methacrylate obtained inExamples 26, 27 and 28 were subjected to elemental analysis using anelemental analyzer (CHN Coder MT-3, product of Yanagimoto SeisakushoCo., Ltd.). Table 3 shows the results.

TABLE 3 material monomer monomer ratio in Ex. ratio (mole %) resultingpolymer (mole %) 26 St:MMA = 66.6:33.3 St:MMA = 61.3:38.7 27 St:MMA =50.0:50.0 St:MMA = 50.6:49.4 28 St:MMA = 33.3:66.6 St:MMA = 32.4:67.6

Table 3 reveals that the process of the invention for preparing livingradical polymers provides random copolymers each having substantiallythe same original material ratio (mole ratio).

EXAMPLE 29 Preparation of poly(methyl methacrylate-b-styrene) diblockpolymer

A 1.01 g quantity (10 mmoles) of methyl methacrylate, 24.8 mg (0.10mmole) of the (1-methyltellanyl-ethyl)benzene prepared in PreparationExample 1 and 28.5 mg (0.10 mmole) of the dimethyl ditelluride preparedin Preparation Example 3 were reacted at 80° C. for 15 hours in a glovebox having its inside air replaced by nitrogen. After the completion ofthe reaction, the reaction mixture was dissolved in 5 ml ofdeuterochloroform, and the solution was thereafter poured into 300 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording 0.809 g (yield 91%) ofpoly(methyl methacrylate). GPC analysis revealed Mn 8500 and PD=1.12.

Next, 425 mg (0.05 mmole) of the poly(methyl methacrylate) (used as amacroinitiator) obtained above and 520 mg (5 mmoles) of styrene werereacted at 100° C. for 24 hours. After the completion of the reaction,the reaction mixture was dissolved in 5 ml of chloroform, and thesolution was thereafter poured into 300 ml of hexane being stirred. Theresulting polymer precipitate was collected by suction filtration anddried, affording 0.7983 g (yield 85%) of poly(methylmethacrylate-b-styrene) diblock polymer. GPC analysis revealed Mn 19000and PD=1.13.

EXAMPLE 30 Preparation of poly(styrene-b-methyl methacrylate) diblockpolymer

A 1.04 g quantity (10 mmoles) of styrene and 24.8 mg (0.10 mmole) of the(1-methyltellanyl-ethyl)benzene prepared in Preparation Example 1 werereacted at 100° C. for 20 hours in a glove box having its inside airreplaced by nitrogen. After the completion of the reaction, the reactionmixture was dissolved in 5 ml of deuterochloroform, and the solution wasthereafter poured into 300 ml of hexane being stirred. The resultingpolymer precipitate was collected by suction filtration and dried,affording a polystyrene in a yield of 95%. GPC analysis revealed Mn 9000and PD=1.15.

Next, 0.05 mmole of the polystyrene (used as a macroinitiator) obtainedabove, 0.505 g (5 mmoles) of methyl methacrylate and 28.5 mg (0.10mmole) of the dimethyl ditelluride prepared in Preparation Example 3were reacted at 80° C. for 16 hours. After the completion of thereaction, the reaction mixture was dissolved in 5 ml of chloroform, andthe solution was thereafter poured into 300 ml of hexane being stirred.The resulting polymer precipitate was collected by suction filtrationand dried, affording a poly(styrene-b-methyl methacrylate) diblockpolymer in a yield of 85%. GPC analysis revealed Mn 13900 and PD=1.25.

EXAMPLE 31 Preparation of poly(methyl methacrylate-b-tert-butylacrylate) diblock polymer

A 1.01 g quantity (10 mmoles) of methyl methacrylate, 24.8 mg (0.10mmole) of the (1-methyltellanyl-ethyl)benzene prepared in PreparationExample 1 and 28.5 mg (0.10 mmole) of the dimethyl ditelluride preparedin Preparation Example 3 were reacted at 80° C. for 15 hours in a glovebox having its inside air replaced by nitrogen. After the completion ofthe reaction, the reaction mixture was dissolved in 5 ml ofdeuterochloroform, and the solution was thereafter poured into 300 ml ofhexane being stirred. The resulting polymer precipitate was collected bysuction filtration and dried, affording 0.809 g (yield 91%) ofpoly(methyl methacrylate). GPC analysis revealed Mn 8500 and PD=1.12.

Next, 425 mg (0.05 mmole) of the poly(methyl methacrylate) (used as amacroinitiator) obtained above and 641 mg (5 mmoles) of t-butyl acrylatewere reacted at 100° C. for 35 hours. After the completion of thereaction, the reaction mixture was dissolved in 5 ml of chloroform, andthe solution was thereafter poured into 300 ml of hexane being stirred.The resulting polymer precipitate was collected by suction filtrationand dried, affording a poly(methyl methacrylate-b-tert-butyl acrylate)diblock polymer in a yield of 57%. GPC analysis revealed Mn 17300 andPD=1.11.

EXAMPLE 32 Preparation of poly(tert-butyl acrylate-b-methylmethacrylate) diblock polymer

A 1.28 g quantity (10 mmoles) of t-butyl acrylate and 24.8 mg (0.10mmole) of the (1-methyltellanyl-ethyl)benzene prepared in PreparationExample 1 were reacted at 100° C. for 24 hours in a glove box having itsinside air replaced by nitrogen. After the completion of the reaction,the reaction mixture was dissolved in 5 ml of deuterochloroform, and thesolution was thereafter poured into 300 ml of hexane being stirred. Theresulting polymer precipitate was collected by suction filtration anddried, affording a poly(t-butyl acrylate) in a yield of 85%. GPCanalysis revealed Mn 7600 and PD=1.15.

Next, 0.05 mmole of the poly(t-butyl acrylate) (used as amacroinitiator) obtained above and 0.505 g (5 mmoles) of methylmethacrylate, 28.5 mg (0.10 mmole) of the dimethyl ditelluride preparedin Preparation Example 3 and 2 ml of trifluoromethylbenzene were reactedat 100° C. for 18 hours. After the completion of the reaction, thereaction mixture was dissolved in 5 ml of chloroform, and the solutionwas thereafter poured into 300 ml of hexane being stirred. The resultingpolymer precipitate was collected by suction filtration and dried,affording poly(tert-butyl acrylate-b-methyl methacrylate) diblockpolymer in a yield of 88%. GPC analysis revealed Mn 19500 and PD=1.35.

EXAMPLE 33 Preparation of poly(methyl methacrylate-b-tert-butylacrylate-b-methyl methacrylate) triblock polymer

A 1.01 g quantity (10 mmoles) of methyl methacrylate, 24.8 mg (0.10mmole) of the (1-methyltellanyl-ethyl)benzene prepared in PreparationExample 1 and 28.5 mg (0.10 mmole) of the dimethyl ditelluride preparedin Preparation Example 3 were reacted at 80° C. for 15 hours in a glovebox having its inside air replaced by nitrogen. Subsequently, 1.28 g (10mmoles) of tert-butyl acrylate was added to the reaction mixture andreacted therewith at 100° C. for 35 hours (Mn 11500, PD=1.09). Thenadded to the reaction mixture were 2.39 g (23 mmoles) of styrene and 5ml of trifluoromethylbenzene, and the mixture was reacted at 100° C. for15 hours. After the completion of the reaction, the reaction mixture wasdissolved in 5 ml of chloroform, and the solution was thereafter pouredinto 300 ml of hexane being stirred. The resulting polymer precipitatewas collected by suction filtration and dried, affording poly(methylmethacrylate-b-tert-butyl acrylate-b-methyl methacrylate) triblockpolymer in a yield of 69%. GPC analysis revealed Mn 21600 and PD=1.27.

EXAMPLE 34 Preparation of poly(methylmethacrylate-b-styrene-b-tert-butyl acrylate) triblock polymer

A 1.01 g quantity (10 mmoles) of methyl methacrylate, 24.8 mg (0.10mmole) of the (1-methyltellanyl-ethyl)benzene prepared in PreparationExample 1 and 28.5 mg (0.10 mmole) of the dimethyl ditelluride preparedin Preparation Example 3 were reacted at 80° C. for 15 hours in a glovebox having its inside air replaced by nitrogen. Subsequently, 1.04 g (10mmoles) of styrene was added to the reaction mixture and reactedtherewith at 100° C. for 24 hours (Mn 18700, PD=1.18). Then added to thereaction mixture were 3.85 g (30 mmoles) of tert-butyl acrylate and 3 mlof trifluoromethylbenzene, and the mixture was reacted at 100° C. for 24hours. After the completion of the reaction, the reaction mixture wasdissolved in 5 ml of chloroform, and the solution was thereafter pouredinto 300 ml of hexane being stirred. The resulting polymer precipitatewas collected by suction filtration and dried, affording a poly(methylmethacrylate-b-styrene-b-tert-butyl acrylate) triblock polymer in ayield of 45%. GPC analysis revealed Mn 21900 and PD=1.18.

EXAMPLE 35 Preparation of poly(styrene-b-methylmethacrylate-b-tert-butyl acrylate) triblock polymer

A 1.04 g quantity (10 mmoles) of styrene, 24.8 mg (0.10 mmole) of the(1-methyltellanyl-ethyl)benzene prepared in Preparation Example 1 werereacted at 100° C. for 20 hours in a glove box having its inside airreplaced by nitrogen. Subsequently, 1.01 g (10 mmoless) of methylmethacrylate and 28.5 mg (0.10 mmole) of the dimethyl ditellurideprepared in Preparation Example 3 were added to the reaction mixture andreacted therewith at 80° C. for 16 hours (Mn 12700, PD=1.30). Then addedto the reaction mixture were 3.85 g (30 mmoles) of tert-butyl acrylateand 3 ml of trifluoromethylbenzene, and the mixture was reacted at 100°C. for 24 hours. After the completion of the reaction, the reactionmixture was dissolved in 5 ml of chloroform, and the solution wasthereafter poured into 300 ml of hexane being stirred. The resultingpolymer precipitate was collected by suction filtration and dried,affording a poly(styrene-b-methyl methacrylate-b-tert-butyl acrylate)triblock polymer in a yield of 32%. GPC analysis revealed Mn 16110 andPD=1.27.

INDUSTRIAL APPLICABILITY

The invention provides a process for preparing living radical polymerswhich realizes precision control of molecular weights and molecularweight distributions under mild conditions. The living radical polymersobtained by the polymerization process of the invention readily permitconversion of terminal groups to other functional groups, are useful forpreparing macromonomers and useful as crosslinking sites and are usableas compatibilizing agents and as materials for block polymers.

1. A mixture of a living radical polymerization initiator represented bythe formula (1) and a compound represented by the formula (2)

wherein R¹ is C₁-C₈ alkyl, aryl, substituted aryl or an aromaticheterocyclic group, R² and R³ are each a hydrogen atom or C₁-C₈ alkyl,and R⁴ is aryl, substituted aryl, an aromatic heterocyclic group, acyl,oxycarbonyl or cyano(R¹Te)₂  (2) wherein R¹ is the same as above.
 2. A mixture according toclaim 1 wherein the living radical polymerization initiator representedby the formula (1) is an organotellurium compound represented by theformula (1) wherein R¹ is C₁-C₄ alkyl, R² and R³ are each a hydrogenatom or C₁-C₄ alkyl, and R⁴ is aryl, substituted aryl or oxycarbonyl,and the compound represented by the formula (2) is a compound wherein R¹is C₁-C₄ alkyl or phenyl.
 3. A process for producing a diblock copolymerwherein a compound of the formula (1) and a compound of the formula (2)are used when a homopolymer is prepared from the first of monomersand/or when the diblock copolymer is subsequently prepared

wherein R¹ is C₁-C₈ alkyl, aryl, substituted aryl or an aromaticheterocyclic group, R² and R³ are each a hydrogen atom or C₁-C₈ alkyl,and R⁴ is aryl, substituted aryl, an aromatic heterocyclic group, acyl,oxycarbonyl or cyano(R¹Te)₂  (2) wherein R¹ is the same as above.
 4. A process for producinga triblock copolymer wherein a compound of the formula (1) and acompound of the formula (2) are used at least once when a homopolymer isprepared from the first of monomers, or when a diblock copolymer issubsequently prepared, or when the triblock copolymer is subsequentlyprepared

wherein R¹ is C₁-C₈ alkyl, aryl, substituted aryl or an aromaticheterocyclic group, R² and R³ are each a hydrogen atom or C₁-C₈ alkyl,and R⁴ is aryl, substituted aryl, an aromatic heterocyclic group, acyl,oxycarbonyl or cyano(R¹Te)₂  (2) wherein R¹ is the same as above.
 5. A process for producinga diblock copolymer comprising mixing together an (meth)acrylic acidester monomer, a living radical polymerization initiator represented bythe formula (1) and a compound of the formula (2) to prepare apoly(meth)acrylate, and subsequently mixing an aromatic unsaturatedmonomer with the product to obtain an (meth)acrylate-aromaticunsaturated monomer diblock copolymer

wherein R¹ is C₁-C₈ alkyl, aryl, substituted aryl or an aromaticheterocyclic group, R² and R³ are each a hydrogen atom or C₁-C₈ alkyl,and R⁴ is aryl, substituted aryl, an aromatic heterocyclic group, acyl,oxycarbonyl or cyano(R¹Te)₂  (2) wherein R¹ is the same as above.
 6. process for producing atriblock copolymer comprising mixing together an (meth)acrylic acidester monomer, a living radical polymerization initiator represented bythe formula (1) and a compound of the formula (2) to prepare apoly(meth)acrylate, subsequently mixing an aromatic unsaturated monomerwith the product to obtain an (meth)acrylate-aromatic unsaturatedmonomer block copolymers, and subsequently mixing an (meth)acrylic acidester monomer or aromatic unsaturated monomer with the copolymer toobtain the triblock copolymer

wherein R¹ is C₁-C₈ alkyl, aryl, substituted aryl or an aromaticheterocyclic group, R² and R³ are each a hydrogen atom or C₁-C₈ alkyl,and R⁴ is aryl, substituted aryl, an aromatic heterocyclic group, acyl,oxycarbonyl or cyano(R¹Te)₂  (2) wherein R¹ is the same as above.